Polyurethane in intimate contact with fibrous material

ABSTRACT

A sprayable polymeric material and a process for preparing the material which contains a fibrous material, dispersed throughout the polymeric material. A restriction free spray nozzle is provided for mixing and spraying the polymeric material having a fibrous material, the nozzle having a restriction free check valve. A reinforced structure, and a method of making the structure are provided, the structure having layers of the polymeric material (both film and foam) containing the fibrous material. A flexible liner is provided of a porous geotextile fabric and a polyurethane composition comprising the fibrous material sprayed over the geotextile fabric.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The invention relates in general to a polymeric compositionscontaining reinforcement fibers, and a process for the preparationthereof, which products are useful for the formulation of reinforcedstructures, coatings, liners, and the like. The invention is alsodirected to an apparatus for and a method of spraying this polymericcompositions, both in the form of a film and a foam.

[0003] 2. Description of Related Art

[0004] A strong, durable, high build rate coating with no volatileorganic compound (VOC) emissions has been desired as a protectivecoating for many years. Attempts at producing a coating having thosecharacteristics has resulted in compromising one or several of desiredproperties. Polyurethane polymers, and coatings made from them, resultfrom the reaction of an isocyanate having an isocyanate terminatedcompound and a polyol having an hydroxyl terminated compound.Polyurethane foams are typically produced by reaction of thepolyisocyanate with the polyol in the presence of a blowing agent.Historically, chlorofluorocarbons such as CFC-11 have been the blowingagents of choice. These agents have been thought to negatively affectthe environment and are being phased out of the polyurethane foammanufacture.

[0005] Low density coatings, when fabricated, tend to have low toughnessor abrasion resistance. Furthermore, most coatings require a significantamount of organic solvent to carry the coating during sprayingapplications, which contributes significantly to the problem of volatileorganic compounds (VOC) emissions. Coating compositions must meet withOccupational Safety and Health Administration and the EnvironmentProtection Agency requirements. Since VOCs are typically toxic,smog-producing and noxious, their continued release can cause adetrimental impact on worker safety and on the environment. Governmentalregulations restrict the amounts and types of VOCs which are permittedto escape into the atmosphere from coating compositions, therefore,there should preferably be no amount of organic solvents present incoating compositions.

[0006] Thick coatings tend to be spongy or brittle and applying thattype of coating to a vertical surface is a slow and tedious process dueto slumping problems or curing/out gassing times required. The majorityof low VOC coatings available at the present time are only acceptablefor thin coating applications (less than 20 mils dry film thickness), orhave an exceedingly long dry time between applications which prohibitsthe successful fabrication of high build rate and/or thick coatings.Another disadvantage associated with many of the products prepared inthe prior art having high viscosities is that application by spraying isoften precluded.

[0007] Polymeric resins containing fillers are known, and are describedin U.S. Pat. No. 5,604,266 to Mushovic. Mushovic discloses apolyester-polyurethane resin material mixed with at least a KEVLAR®filler (manufactured by DuPont). The KEVLAR pulp filler is added to thepolyol reactant of the polyurethane. The polyurethane mixture ofMushovic was then poured into a mold. Mushovic does not disclose orsuggest a sprayable polymeric composition containing reinforcing fibers.In the present invention, polymer compositions containing KEVLAR orother reinforcing fibers can be sprayed, while maintaining homogeneityof the composition, necessary for the spray application. Polymercompositions that can be sprayed are more flexible in the field, theycan conform to complex shapes and surface details. In order to spray apolymeric composition comprising a reinforcing fiber, such as KEVLAR,SPECTRA® (owned and manufactured by Allied-Signal, Inc., Delaware,U.S.A.), carbon fullerenes and nanotubes, not only must the compositionbe mixed properly but also requires a modification be made to thedispensing apparatus, i.e. the spray gun. U.S. Pat. No. 4,857,569 toCotts et al., discloses a polymer alloy composition prepared byintimately mixing one or more polyurethane components with selectedreinforcing amounts of rod-like aromatic polyamide components (e.g.KEVLAR). However, the compositions of Cotts must be formed either byblending two individual solutions of the polyurethane and rod-likepolyamide components in a common or mutually compatible solvent, or bypolymerizing the polyurethane components in a solvent, which is itself asolution of the rod-like polyamide component in a suitable solvent.Thus, the KEVLAR reinforcing fiber must be dissolved in a solvent, e.g.,a solution of polyparaphenyleneterephthalamide. U.S. Pat. Nos.4,599,401; 4,629,779; 4,707,535; and 4,725,653 to Koleske; U.S. Pat. No.4,857,579 to Domeier and U.S. Pat. No. 4,233,205 to O'Connor disclosepolyurethane elastomers or other polyurethane products containing KEVLARfibers. U.S. Pat. No. 5,610,224 to DePue et al., discloses an elasticand high strength material formed from polyurethane and aromaticpolyamide. Japanese Patent 53-34884 to Masanobu et al., discloses acomposite material prepared by curing and bonding an aromatic polyamidefiber and a thermosetting resin with a specific lactam compound and anisocyanate compound.

[0008] A hybrid liner is described in U.S. Pat. No. 4,956,397 toRogowski et al., which describes an insulating solid rocket liner madefrom polyurethane rubber and KEVLAR pulp or fibers, specificallyfibrillated fibers. U.S. Pat. Nos. 4,034,138 and 4,095,404 to Babayanand U.S. Pat. No. 5,120,905 to Cousin et al., all disclose polyurethanematerial impregnated or coated with aromatic polyamide fibers. U.S. Pat.No. 5,167,352 to Robbins and U.S. Pat. No. 5,419,139 to Blum et al.,both disclose a double wall tank system or a composite cryogenic tankcoated or lined with polyurethane and KEVLAR. Blum specificallydiscloses a tank lined with a laminate of film layers, each having avacuum deposited metalized coating.

[0009] A problem associated with adding a reinforcing fiber, such asKEVLAR, to a polyurethane resin solution has been that the fibersseparate out from the polyurethane reaction components, or deterioratebecause of the solvents or catalysts in the reaction components, makingit impossible to exhibit the intended properties and strength andstability of the added reinforcing fibers. Accordingly, it hasconventionally been necessary to agitate the reaction components so asto be uniformly mixed and dispersed, before its use, i.e., before thepolyisocyanate and polyol components are mixed together to cause thereaction. Thus, polyurethane resin formed from conventional polyurethanereaction components containing reinforcing fibers cannot be sprayed.

[0010] Conventional spray gun assemblies have spring loaded check valvesfor restricting the flow of two-part reactive polymers. See FIGS. 1 and2. U.S. Pat. No. 5,810,254 to Kropfield, which describes two premixingchambers, that receive the polymer reaction components, each chamberhaving an actuating valve for controlling the flow of the componentsthrough the premixing chambers. Since two part polyurethanes require avery specific percentage ratio of the two material components, anysignificant variation will not produce a polyurethane with the desiredcure effectively or quickly, and may not have the desired durability.

[0011] The ideal polymer for use as a coating or liner would containreinforcing fibers and other fillers that could be sprayed, would beeasy to use, quick to activate, and have a long service life. Polymersthat do not have any volatile organic content and do not leak hazardousmaterials, having zero toxicity, are also necessary for use in coatingsand liners. New methods for greatly reducing or eliminating VOCs duringthe application of such coatings are urgently needed to prevent workerinjury and comply with current and pending environmental regulations.Also of great importance is the cost, performance and durability of suchpolymer formulations. Currently, there does not exist a method of makinga polymer composition that satisfies all these criteria.

BRIEF SUMMARY OF THE INVENTION

[0012] The present invention provides a solvent-free, sprayablepolymeric material and a process for preparing a polymer with a fibrousmaterial by providing a predetermined amount of fibrous material,providing reaction components comprising a polyol and an isocyanate, ora combination of a polyurethane with a polyurea, polyester, or epoxy,heating the reaction components, adding the fibrous material to thepolyol component, the isocyanate component, or both, and then reactingthe reaction components. Another embodiment of the present inventionprovides a restriction free spray nozzle for mixing and spraying a firstreactive polymeric material with a second reactive polymeric material,at least one of the reactive polymeric materials containing a fibrousmaterial, so as to form a two part polymer, the nozzle comprising: arestriction free check valve without springs, a hose for conveying firstand second polymeric materials to a ball valve, the nozzle spraying amixture of the first and second materials from the check valve onto asurface. The nozzle has a large diameter tip of about 0.21-0.45Thousands (thousands of an inch). A mixture of the first and secondmaterials goes through a mixing block and through a static mixer throughthe nozzle and onto a surface. Another embodiment of the presentinvention provides a reinforced structure and a method of making thestructure. The structure comprises a first and second layer ofpolyurethane resin containing from about 0.5 to 30% by weight of afibrous material sandwiching a layer of polyurethane foam containingfrom about 0.5 to 30% by weight of a fibrous material. A furtherembodiment of the present invention provides a flexible liner whichcomprises a porous geotextile fabric, a polyurethane compositioncomprising a fibrous material sprayed over the geotextile fabric,forming a monolithic membrane with the geotextile fabric.

[0013] The products of the present invention are applicable to buildingelements and articles of manufacture, in particular composite buildingmaterials, e.g., coated panel boards, which are lightweight, or asgeotextile liners used to line land fills, or for lining/relining pipes.Liners of the present invention have a substantially fluid-tight or leakproof construction, which gives them various useful applications such asimproved enclosures for fluid-confining means. Thus, the reinforcedfiber polyurethane of the present invention would also have applicationin the wastewater industry, where polyurethanes have been usedextensively since the 1970's. The properties of polyurethanes that areamenable to use in the potable water, hazardous waste, chemical andwastewater industries are their impermeability, resistance to microbialattack, excellent adhesion and abrasion resistance, flexibility, andunlimited film build. Objects made of steel, iron, plastics andconcrete, or objects previously lined with other coatings, may be linedwhile maintaining the advantageous properties of the polymer, e.g.,polyurethanes.

[0014] The composition of the present invention can be sprayed onto avariety of surfaces to provide abrasion and corrosion resistance, theseamless coating being resistant to many corrosion causing chemicals.Since there is no solvent to evaporate, several cost and time savingadvantages accrue. Sandblasting surface preparation of the surface to becoated is avoided, thus, requiring less work, expense and time beforeapplication and eliminating waste disposal of the surface preparationmaterials and any prior coating that was removed. The compositions allowgreater thickness per pass, typically 30-40 mils, (solvent systemstypically achieve about 4 up to 20 mils), no time lag between coats(solvent systems tend to run); much shorter tack-free times; noinflammable or toxic solvent hazards; no solvent attack on sensitivesurfaces; and good adhesion to various substrates. The composition issprayable at temperatures of about 240° F. and above, preferably 140° F.and is easily mixed. Moreover, it was unexpectantly found that thecoating comprising KEVLAR reinforced fibers was sandable and, thus,easily repairable.

[0015] Foam having reinforced fiber can be used to seal cracks. If thecrack already has water in it, the reinforced resin (without addingwater) can be sprayed into the crack, react with the water in the crack,creating a foam. Thus, the composition can be applied in concretereservoirs and parking lots to fill cracks.

[0016] It was discovered that polymeric compositions and products coatedwith the composition did not have the problems associated withconventionally coated products, such as blistering and leaching ofvolatile organic compounds. Blisters appear in conventional polymercoatings as raised, localized swellings of the coating, often occurafter immersion in liquids, and a viscous acidic liquid is expelled whenruptured. The coating of the present invention solves this problembecause it lacks VOCs.

[0017] The composition of the present invention can also be used tomanufacture pipes. Water flowing inside pipes made with the compositionof the present invention, comprising KEVLAR, do not have their waterflow drag/friction affected by the KEVLAR fibers contained in thecomposition. Reinforced polyurethane pipes have greater strength and areable to withstand increased, otherwise bursting, pressure. The lowerfriction inside the pipes decreases costs to supply water to homes.

[0018] Compositions containing specific reinforcing fibers may be usedin applications requiring the properties provided by those fibers andthe polymeric composition. For example, ceramic and carbon fiberscombined with polyurethane compositions can be used in applicationsrequiring control of thermal expansion.

[0019] Theses and other features, aspects, and advantages of the presentinvention will become better understood with regard to the followingdetailed description, appended claims, and accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020]FIG. 1 is a perspective view of a mixing block of the prior art;

[0021]FIG. 2 is an exploded perspective view of the mixing block of FIG.1, showing the elements thereof in greater detail; and

[0022]FIG. 3 is an elevational view of the restriction free spray nozzleof the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0023] Any of the polyols used in the art to prepare polyurethanes andpolyurea-containing polyurethanes or mixtures thereof can be used, forexample: a polyol chosen from a variety of —OH terminated polyetherssuch as the polyoxyalkylene polyols having 2-4 hydroxyl groups and wherethe alkylene group has 2-6 carbon atoms, obtained by polymerization ofan alkylene oxide, such as ethylene oxide, propylene oxide, or butyleneoxide, with a glycol; polyethers having higher functionality obtained byreaction with a triol or higher polyol, such as glycerine,trimethylolpropane, and pentaerythritol; and polypropylene-oxide triol,having a preferable molecular weight range of about 300 to 20,000, mostpreferably 500 to 5000; and aromatic or aliphatic amine-based polyols,and sorbitol based polyether polyols.

[0024] The isocyanate component of the polymeric composition may be adiisocyanate or a polyisocyanate. While any suitable polyisocyanate canbe used in the foam-making process, readily available industrialpolyisocyanates are particularly preferred. Various elastomericpolyurethanes are available from Prime Coatings Incorporated, located inHuntington Beach, U.S.A., under the trademark Utilithane-1600. Otherexamples of suitable diisocyanates and polyisocyanates useful for makingpolyurethane foams comprise aromatic, aliphatic and cycloaliphaticpolyisocyanates, among others. Representative members of these compoundscomprise diisocyantes such as 4,4′-Diphenylmethane-diisocyanate,hexamethylene diisocyanate; m-xylylene diisocyanate; toluenediisocyanate and/or any of its isomers such as 2.4-toluene diisocyanateor commercially available blends of the 2,4- and 2,6-isomers such as the80:20 and 65:35 blends; polymethylene polyphenylisocyanate; m-phenylenediisocynate; p-phenylene diisocyanate; 3,3′-dimethyl-4,4′-diphenyldiisocyanate; methylenebis (2-methyl-p-phenylene) diisocyanate;3,3′-dimethoxy-4,4′-biphenylene diisocyanate;2,2′4,4′-tetramethyl-4,4′-biphenylene diisocyanate;3,3′-dimethyl-4,4′-diphenylmethane diisocyanate;4,4′-diphenylisopropylidene diisocyanate; 1,5′-naphthylene diisocyanate;and polymethylene polyphenylisocyanate. The ratio of equivalents ofisocyanates, side A components, to polyols, side B components is fromabout 10 to 1 by volume, preferably from about 3 to 1, most preferablyfrom about 1 to 1.

[0025] The structure of KEVLAR is unique in that it is an organic fiberthat is crystalline with a high degree of orientation. KEVLAR pulp isproduced by fracturing this crystalline structure. Pulp products arevery short, highly fibrillated fibers. The amount of KEVLAR used isbased on its total weight percent of the polymeric composition (themixture of component/side A and component/side B reagents), and ispreferably added in the amount of about 0.50 weight % to 30 weight % ofthe total weight percent of the polymeric composition, preferably about0.50 weight % to 1.00 weight %, most preferably about 0.50 weight % to0.75 weight %, for applications using a spray gun. The amount of addedreinforcing fiber, e.g., KEVLAR, may be easily increased for handapplications and the higher end of the previously disclosed range may beused, e.g., about 30 weight %. If the KEVLAR is separately added tocomponent A and component B, the KEVLAR added to component A plus theKEVLAR added to component B is about 0.50 weight % to 30 weight % of thetotal weight percent of the polymeric composition, preferably about 0.50weight % to 0.75 weight %. When the KEVLAR is added to both components Aand B, it is preferably added to component A in an equal weight percentamounts to that added to component B. However any amount may be added tothe components individually as long as the total amount of KEVLAR addedis about 0.50 weight % to 30 weight % of the total weight percent of thepolymeric composition. Other fibers could be used to substitute for theKEVLAR, such as SPECTRA, glass and ceramic fibers, carbon fullerenes,and carbon nanotubes and can be added in the same amounts.

[0026] Catalysts can be added which promote the formation ofpolyurethane by reaction of the isocyanate groups and hydroxy groups.For example, amine compounds, such as triethanolamine,triethylenediamine, N-methylmorpholine, tetramethyl-1,4-butanediamine,N-methylpiperazine, dimethylethanolamine, and diethylethanolamine,triethylamine; and organometallic compounds, such as stannous octanoate,dibutyltin dilaurate, and dibutyltin di-2-ethylhexanoate. Thesecatalysts may be used alone or in combination with one another. Amountsused are 1:1-10:1 by weight ratio of the catalyst: polymeric compositioninclusive of the reinforcing fibers.

[0027] It is often desirable to employ minor amounts of certain othercompounds in preparing the polymer composition, such as: one or morecatalysts, surfactants, fire retardants, preservatives, pigments(including titanium or aluminum dioxide, and high UV absorbingultra-fine titanium dioxide), antioxidants, anti-microbial agents,filler, and anti-static agents, powdered tungstun. Amounts used can beup to 25% by volume of the total weight of the polymer composition.

[0028] Spraying the polymeric film/foam compositions of the presentinvention begins when the fibrous material is pre-weighed to the totalweight of polymeric composition (e.g., the polyurethane) desired, asdiscussed above. It is preferable to use fibrous material that is dry,such as by heating it to a temperature of from about 140° to 160° F.,prior to adding the fibrous material to the reaction components A and/orB. Component A and B are heated to a temperature of about 160° F. to250° F. About 10 Volume % of Component A is added with the pre-weighedfibrous material, or 10 Volume % of Component B is added to thepre-weighed fibrous material, or both components are added/blended withthe predetermined total weight % of the fibrous material for aboutfifteen minutes under anhydrous conditions, preferably under an inertatmosphere such as a nitrogen blanket. The adding of the fibrousmaterial to the polyol, the isocyanate, or both, is such that thefibrous material is mixed randomly within the polyol, the isocyanate, orboth. The separate components, one or both of which contain the fibrousmaterial are packaged under anhydrous conditions, preferably under aninert atmosphere such as a nitrogen blanket, until ready foruse/application. If the composition of the present invention is sprayedin multiple applications, it is preferable to follow the firstapplication while it is still in a soft liquid phase, whereby to allowthe polymer to cross-link, enabling the fibrous material to embed inboth the layer of the first application and any following applications.

[0029] Application of the polymeric composition begins when component Areagent is supplied by pump to a metering unit, or a metering pump.Component B containing polyol, catalysts, or surfactants is thenprepared according to a defined formulation in a mix tank. Either orboth component A or B contains the fibrous material. Any additionalblowing agents, e.g. water or an alcohol/water mixture may be eitheradded to component B, prior to its reaction with component A, or may beadded to the mixture of component A and component B. Component B is alsosupplied by pump to a metering unit, or a metering pump. The meteringpumps boost the pressure generally to 2000 to 2500 psi and control theflow of components A and B to a precise ratio as determined by thedesired chemistry. The ratio of isocyanates, side A components, topolyols, side B components is from about 10 to 1 by volume, preferablyfrom about 3 to 1, most preferably from about 1 to 1. The pumps delivercomponents A and B to at least one mixing block. Inside the mixingblock, components A and B are statically mixed at high pressure, whichresults in intimate mixing of the components. The mixed componentstravel through an input hose (12) to the ball valve (10) through therestriction free check valve (20), a check valve without the spring (22)of the prior art check valve, through the spray tip (30), seen in FIG.3. The pot life or working time of the mixed polymeric composition isvariable, but is typically short. The mixed chemicals begin to react inabout 3 seconds following mixing and completing reaction in about 3-30minutes.

[0030] The polymeric composition of the present invention may be sprayedin any thickness, typically of about 2000 mils to 10 mils in oneapplication, depending on the project needs. The polymeric foam of thepresent invention can be sprayed into a mold, either in normalatmospheric conditions or under 2-3 atm of pressure.

[0031] The geotextile fabric is porous such that the polyurethane canfill in the pores and it becomes one-layer.

[0032] Surface Preparation

[0033] Conventional coating processes require expensive and laborintensive surface preparation. For example, steel surfaces typicallyrequire abrasive sand blast cleaning to near white, which necessitatesexpensive removal of oftentimes hazardous materials. However, thepresent invention requires little or no surface preparation.Deteriorated concrete surfaces should be prepared by high-pressure waterblasting to a sound concrete surface that is free of oil, grease, orexisting coatings.

[0034] The following examples are given to illustrate the invention.

EXAMPLE 1

[0035] KEVLAR was pre-weighed to the 0.75 weight percent of the totalweight desired of the final polyurethane material. The side A reactioncomponent, a diisocyanate (4,4′ Diphenylmetane-diisocyanate) and theside B reaction component, a blend of hydroxy-terminated polyols foundin Utilithane 1600 manufactured by Prime Coatings, Inc., HuntingtonBeach, U.S.A., were heated to a temperature of about 160° F. Under aninert atmosphere of nitrogen, ten percent by volume of the diisocyanatewas added to and mixed for about fifteen (15) minutes with thepre-weighed KEVLAR pulp, in order to wet the KEVLAR fibers. Theremaining amount of the diisocyanate was added to the diisocyanatecontaining the pre-wetted KEVLAR fibers, and was mixed for about thirty(30) minutes under an inert atmosphere of nitrogen. The remaining amountof polyol was added to the polyol containing the pre-wetted KEVLARfibers, and was also mixed for about thirty (30) minutes under an inertatmosphere of nitrogen. The diisocyanate and polyol containing KEVLARwere packaged separately under an inert atmosphere of nitrogen untilneeded for application. The diisocyanate and the polyol were in an about1:1 ratio by volume.

EXAMPLE 2

[0036] The procedures of Example 1 were followed substituting 1.0 weight% KEVLAR pulp for the 0.75 weight %.

EXAMPLE 3

[0037] The procedures of Example 1 were followed substituting bringingthe temperatures of the diisocyanate and polyol reagents to about 250°F., prior to adding the pre-weighed KEVLAR pulp.

EXAMPLE 4

[0038] The procedures of Example 1 were followed adding the step ofdry-heating the pre-weighed KEVLAR pump to a temperature of about 160°F., prior to adding to the 10% diisocyanate and polyol reagents.

EXAMPLE 5-8

[0039] The procedures of Example 1 can be followed by substituting,respectively, about 0.5 to 0.75 weight % of the following: highmolecular weight polyethylene fibers, such as SPECTRA fibers;fullerenes; nanotubes; ceramic fiber, for the KEVLAR pulp fibers.

EXAMPLE 9

[0040] The procedures of Example 1 were followed substituting 30 weight% KEVLAR for the 0.75 weight % KEVLAR.

EXAMPLE 10

[0041] The procedures of Example 1 were followed by substituting thestep of adding the pre-weighed KEVLAR pulp to 100% of the diisocyanateand polyol reagents and blending for about thirty (30) minutes, for thesteps of adding the KEVLAR to ten (10)% of the diisocyanate and polyolreagents.

EXAMPLE 11

[0042] The procedures of Example 1 were followed by substituting thestep of adding the pre-weighed KEVLAR pulp to ten % of the diisocyanatereagent only, for the step of adding the pre-weighed KEVLAR pulp to ten% of the diisocyanate and ten % of the polyol reagents.

EXAMPLE 12

[0043] The procedures of Example 1 were followed by substituting thestep of adding the pre-weighed KEVLAR pulp to ten % of the polyolreagent only, for the step of adding the pre-weighed KEVLAR pulp to ten% of the diisocyanate and ten % of the polyol reagents.

EXAMPLE 13

[0044] The diisocyanate and polyol reagents containing KEVLAR made fromthe procedures of Example 1 were followed to create the polyurethanefoam containing KEVLAR of the present invention. A predetermined amountof water (e.g., 0.5% by volume) was added to the polyol reactioncomponent, creating a foam. The predetermined amount depends on theneeded density of the resulting foam.

EXAMPLE 14

[0045] The procedures of Example 13 can be followed substituting thestep of adding water to the polyol reaction component for the step ofinjecting water as a third component, before the mixer, at an equalpressure to the two other reagents (the polyol and the isocyanate).

EXAMPLE 15

[0046] A porous geotextile sheet of about ⅛″ to {fraction (3/16)}″manufactured by Geotextile was used to line a concrete surface. Theconcrete surface was prepared by pressure wash. The KEVLAR containingpolyurethane film of the present invention was sprayed onto the porousgeotextile mat which formed a monolithic membrane with the geotextilemat. The perimeter edges of the sheet were sprayed with the polyurethaneto attach the sheet to the surface.

EXAMPLE 16

[0047] A method of applying the composition of the present invention toline an old tank concrete was carried out. The surface of the tank wasprepared by pressure washing (<1000 psi) with water to clean thesurface. A thin layer of about 20 mils of polyurethane without thereinforcing fiber was sprayed onto the tank surface, which served toseal in volatile organic compounds leaking from the previous liner. Thediisocyanate composition containing 1.00 weight % KEVLAR was supplied bypump to a metering pump. The polyol composition containing 1.00 weight %KEVLAR was also supplied by pump to a metering pump. The metering pumpsboosted the pressure to about 2000 to 2500 psi and controlled the flowof the diisocyanate and polyol to a ratio of about 1:1. The pumpsdelivered the diisocyanate and polyol containing KEVLAR to at least onefoam/film mixhead. Inside the mixhead, the Components A (diisocyanate)and B (polyol) were impinged against each other at high pressure, whichresulted in intimate mixing of the components, forming a sprayablepolyurethane containing KEVLAR. The polyurethane containing KEVLAR wasthen sprayed in a single application over the tacky underlying layer ofabout 20 mils, thereby fusing with the underlying layer. Thepolyurethane layer containing the KEVLAR was applied in a coating ofabout 100 mils.

EXAMPLE 17

[0048] A reinforced polymeric panel was manufactured. A sheet ofpolyethylene was laid down in a container. 20 mils of the compositionmade in Example 1 was sprayed on top of the polyethylene sheet, whilestill tacky (about 1 minute), a polyurethane foam of Example 13 wassprayed at about 20 to 100 mils. The foam was sprayed while the resinlayer was still tacky so that the polyurethane layers cross-linked andthe KEVLAR fibers contained in both the resin and foam, embedded withinboth layers. The polyethylene sheet was removed (peeled off) and thepanel was planed.

EXAMPLE 18

[0049] A reinforced construction panel was made by spraying a layer ofpolyurethane (as described in Example 1) in a mold 20-2000 mils thick,while it was still tacky (about 3 minutes) the polyurethane foam ofExample 13 was sprayed at a predetermined thickness. Thickness isdependent on the application of the panel are there are no limits to howthick to spray the foam. The polyurethane resin material containedKEVLAR, and was sprayed on both the top and bottom sides of the panel.

EXAMPLE 19

[0050] The panels of Example 17 and 18 can be pre-threaded for futureuse in attaching the panels to other objects. A fastener is attached tothe polyurethane layer prior to spraying the polyurethane foam. Sprayingthe polyurethane foam. After the foam is set, the fastener is removed,leaving a hole of a predetermined diameter, for use subsequentattachment of the panel.

EXAMPLE 20

[0051] Pipes can be made of the polymeric resin of Example 1. A mold ofpredetermined length and diameter is placed on a lathe. A hose can besuspended above the lathe and mold and to run parallel to the length ofthe mold. The hose either can have predetermined spaced spay tips forallowing the polymeric material to be sprayed or can have at least onespray tip which is moved above and along the length of the mold. Thepolymeric material of Example 1 can be sprayed through the spray tips,for a predetermined amount of time while the mold is spun on the latheto form a pipe of predetermined thickness.

[0052] The following references are incorporated herein by reference:U.S. Pat. No. 5,604,266 to Mushovic; Cotts et al. U.S. Pat. No.4,857,569; U.S. Pat. Nos. 4,599,401; 4,629,779; 4,707,535; and 4,725,653to Koleske; U.S. Pat. No. 4,857,579 to Domeier; U.S. Pat. No. 4,233,205to O'Connor; U.S. Pat. No. 5,610,224 to DePue et al.; Japanese Patent53-34884 to Masanobu et al.; U.S. Pat. No. 4,956,397 to Rogowski et al.;U.S. Pat. Nos. 4,034,138 and 4,095,404 to Babayan; U.S. Pat. No.5,120,905 to Cousin et al.; U.S. Pat. No. 5,167,352 to Robbins; U.S.Pat. No. 5,419,139 to Blum et al.; and U.S. Pat. No. 5,810,254 toKropfield.

[0053] Although the foregoing invention has been described in somedetail by way of illustration and example for purposes of clarity andunderstanding, it will be obvious that various modifications and changeswhich are within the knowledge of those skilled in the art areconsidered to fall within the scope of the appended claims.

1. A process for the preparation of a sprayable polymeric materialhaving a fibrous material, comprising: a) providing a predeterminedamount of fibrous material; b) providing reaction components comprisinga polyol and an isocyanate; c) heating the reaction components; d)adding the fibrous material to the polyol component, the isocyanatecomponent, or both; and e) reacting the reaction components, whereby tocreate the polymeric material.
 2. The process of claim 1, furthercomprising heating the fibrous material to a temperature from about 140°F. to 160° F., prior to adding the fibrous material to the reactioncomponents.
 3. The process of claim 1, wherein the fibrous material issubstantially dry.
 4. The process of claim 1, further comprising, priorto adding the fibrous material, pre-wetting the fibrous material to (i)about 10% by volume of the polyol component, (ii) about 10% by volume ofthe isocyanate component, or (iii) about 10% of both componentscombined.
 5. The process of claim 1, wherein the fibrous material is anaramid, high molecular weight polyethylene, fullerene, nanotube, ceramicfiber, or mixtures thereof.
 6. The process of claim 5, wherein thearamid fiber is KEVLAR pulp.
 7. The process of claim 1, wherein thepredetermined amount of fibrous material is from about 0.5 weightpercent to 1.0 weight percent of the total weight of the composition. 8.The process of claim 1, wherein the heating of the reaction componentsis from about 160° F. to 250° F.
 9. The process of claim 1, wherein thepolyol component and the isocyanate component are provided in a 1:1ratio by volume.
 10. The process of claim 1, further comprising addingwater to the polymeric material, whereby to create a matrix of closedcell polyurethane.
 11. The process of claim 10, further comprisingapplying pressure to closed cell polyurethane.
 12. The process of claim1, wherein the adding of the fibrous material to the polyol, theisocyanate, or both, is by mixing, whereby to randomly locate thefibrous material within the polyol, the isocyanate, or both.
 13. Aprocess for the preparation of a composite of a sprayable polymer resinhaving a reinforcing fiber, comprising adding the reinforcing fiber to afirst polymeric material solution and to a second polymeric materialsolution, reacting the first and second solutions, whereby thereinforcing material is incorporated homogeneously without causingseparation during the curing reaction between the first and secondpolymeric material solutions.
 14. The process for the preparation of asprayable polymeric material having a fibrous material, comprising: a)providing a predetermined amount of fibrous material; b) providing atleast two reaction components, wherein the components contain novolatile organic compounds and are polyurethane, polyester, epoxy,polyurea; c) heating the reaction components; d) adding the fibrousmaterial to the polyol component, the isocyanate component, or both; ande) reacting the reaction components, whereby to create the polymericmaterial.
 15. A restriction free spray nozzle for mixing and spraying afirst reactive polymeric material with a second reactive polymericmaterial, at least one of the reactive polymeric materials containing afibrous material, forming a two part polymer comprising: a restrictionfree check valve without springs, a hose for conveying said first andsecond polymeric materials to a ball valve, said nozzle spraying amixture of the first and second materials from said check valve onto asurface.
 16. The spray nozzle of claim 15, wherein the fibrous materialis an aramid, high molecular weight polyethylene, fullerene, nanotube,ceramic fiber, or mixtures thereof.
 17. The spray nozzle of claim 16,wherein the aramid fiber is KEVLAR pulp.
 18. A reinforced structurecomprising a first and second layer of polyurethane resin containingfrom about 0.5 to 1.0% by weight of a fibrous material sandwiching alayer of polyurethane foam containing from about 0.5 to 1.0% by weightof a fibrous material.
 19. The reinforced structure of claim 18, whereinthe fibrous material is an aramid, high molecular weight polyethylene,fullerene, nanotube, ceramic fiber, or mixtures thereof.
 20. Thereinforced structure of claim 19, wherein the aramid fiber is KEVLARpulp.
 21. The reinforced structure of claim 18, wherein the first andsecond layers of polyurethane resin are about 100 mils.
 22. Thereinforced structure of claim 18, further comprising a panel betweensaid first layer of polyurethane foam and a second layer of polyurethanefoam.
 23. A method of coating a reinforcement structure having a top anda bottom side with a polyurethane composition comprising: a) providing apredetermined amount of fibrous material; b) providing reactioncomponents comprising a polyol and an isocyanate; c) heating thereaction components; d) mixing the fibrous material with the polyol, theisocyanate, or both; e) reacting the reaction components, whereby tocreate a polymeric resin; f) spraying the top of the reinforcementstructure with a polymeric foam containing a second fibrous material;and g) spraying the top of the reinforcement structure with thepolymeric resin, prior to cure of the polymeric resin.
 24. The method ofclaim 23, further comprising spraying the bottom side of thereinforcement structure with the polymeric foam.
 25. The method of claim24, further comprising spraying the bottom side of the reinforcementstructure with the polymeric resin.
 26. The method of claim 23, whereinthe step of reacting the reaction components is performed in an inertatmosphere.
 27. The method of claim 23, wherein the first and secondfibrous materials are aramid, high molecular weight polyethylene,fullerene, nanotube, ceramic fiber, or mixtures thereof.
 28. The methodof claim 27, wherein the aramid fiber is KEVLAR.
 29. The method of claim23, wherein the fibrous material is from about 0.5% to 1.0% by weight ofthe polymeric resin.
 30. The method of claim 23, wherein the heating isfrom about 160° F. to 250° F.
 31. The method of claim 23, wherein thepolyol and the isocyanate are provided in about a 1:1 ratio by volume.32. The method of claim 23, further comprising applying pressure to thereaction components.
 33. The method of claim 23, wherein thereinforcement structure is sprayed with about 100 mils of the polymericresin.
 34. A sprayable polyurethane composition comprising from about0.5% to 30% by weight of a fibrous material, wherein the polyurethane issolvent-free and is the reaction product of a polyol and apolyisocyanate.
 35. The composition of claim 34, wherein the fibrousmaterial is an aramid, high molecular weight polyethylene, fullerene,nanotube, ceramic fiber, or mixtures thereof.
 36. The composition ofclaim 35, wherein the aramid fiber is KEVLAR pulp.
 37. A flexible linercomprising: a) a porous geotextile fabric; and b) a polyurethanecomposition comprising a fibrous material sprayed over said porousgeotextile fabric, whereby to form a monolithic membrane with thegeotextile fabric.
 38. The flexible liner of claim 37, wherein thepolyurethane is sprayed at about 100 mils.
 39. The flexible liner ofclaim 37, wherein the fibrous material is an aramid, high molecularweight polyethylene, fullerene, nanotube, ceramic fiber, or mixturesthereof.
 40. The flexible liner of claim 37, wherein the aramid fiber isKEVLAR pulp.
 41. A process for the preparation of a flexible linercomprising: a) providing a sheet of a porous geotextile fabric having aperimeter edge; and b) spraying a polyurethane composition comprising afibrous material onto said porous geotextile fabric, whereby to form amonolithic membrane with the geotextile fabric.
 42. The process of claim41, wherein the spraying of the polyurethane is about 100 mils.
 43. Theprocess of claim 41, wherein the fibrous material is an aramid, highmolecular weight polyethylene, fullerene, nanotube, ceramic fiber, ormixtures thereof.
 44. The process of claim 43, wherein the aramid fiberis KEVLAR pulp.
 45. The process of claim 41, further comprisingproviding an object to be lined.
 46. The process of claim 45, furthercomprising attaching the geotextile fabric to the object with anadhesive, prior to spraying the polyurethane composition, wherein theperimeter edge of the geotextile fabric is not tacked to the object toallow gas to escape.